CN104507565A - Water-absorbing resin, water-absorbing body, and water-absorbing product - Google Patents

Water-absorbing resin, water-absorbing body, and water-absorbing product Download PDF

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Publication number
CN104507565A
CN104507565A CN201380037722.8A CN201380037722A CN104507565A CN 104507565 A CN104507565 A CN 104507565A CN 201380037722 A CN201380037722 A CN 201380037722A CN 104507565 A CN104507565 A CN 104507565A
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water
absorbing resins
absorbing
crosslinking agent
mole
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CN201380037722.8A
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CN104507565B (en
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渡边彩佳
近藤公彦
鹰取润一
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Sumitomo Seika Chemicals Co Ltd
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Seitetsu Kagaku Co Ltd
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/45—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the shape
    • A61F13/49—Absorbent articles specially adapted to be worn around the waist, e.g. diapers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/14—Organic medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/32—Polymerisation in water-in-oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Materials Engineering (AREA)
  • Hematology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

One purpose of the present invention is to provide a water-absorbing resin having excellent water absorption characteristics and being capable of improving the shape-retaining characteristics of a water-absorbing body when used in the water-absorbing body. A water-absorbing resin obtained by performing reversed phase suspension polymerization of a water-soluble ethylenically unsaturated monomer in a hydrocarbon dispersion medium, using a radical polymerization initiator, said resin being capable of having both excellent absorption performance and shape retention in a water-absorbing body using the water-absorbing resin, as a result of fulfilling the conditions of: (1) having a physiological saline retention of at least 38g/g; (2) having a physiological saline absorption ability of at least 15 ml/g under a 4.14 kPa load; and (3) having a tan (delta) for a gel swollen by a factor of 50 of at least 2.10*10<-2>.

Description

Water-absorbing resins, absorber and absorbent commodity
Technical field
The present invention relates to a kind of water-absorbing resins and use absorber and the absorbent commodity of this water-absorbing resins.Be described in more detail, relate to a kind of physiological saline water holding capacity having excellence concurrently, high physiological saline water absorbing capacity under a load and the viscoelastic water-absorbing resins of excellence, and use absorber and the absorbent commodity of this water-absorbing resins.
Background technology
Water-absorbing resins, is widely used in recent years in the various field such as industrial goods, materials and equipments of the hygienic material of disposable diaper or physiological articles etc., agronomy material, water-stop or the anti-caking distillate medicinal water etc. of water-loss reducer or native Reel modifying agent etc.In these areas, the hygienic material of disposable diaper or physiological articles etc. is particularly used for.
For this water-absorbing resins, the cross-linking agent etc. of saponified, the acrylate moiety corrective polymer of the hydrolyzable thing of such as known Starch-Acrylontirile Graft Copolymer, the corrective of starch-acrylic acid graft polymer, ethyl acetate-acrylate copolymer.
On the other hand, the absorbent commodity of disposable diaper, sanitary napkin, incontinence protection pad etc. is primarily of being configured in central part, absorbing the body fluid of the urine, menses etc. that go out from body excretes and the absorber kept, at the surficial sheets (top-sheet) of the liquid permeability configured with Body contact side, and form in the liquid-impermeable back-sheet (back sheet material) that the opposite side with Body contact configures.In addition, absorber is made up of the hydrophilic fibre of paper pulp etc. and water-absorbing resins usually.
Absorber keeps liquid by water-absorbing resins after temporarily being kept with hydrophilic fibre by the liquid of being come in by surficial sheets.Usually, in the liquid absorption amount improving absorber, the increase amount of water-absorbing resins, the amount of corresponding minimizing hydrophilic fibre are effective.But, when increasing the amount of water-absorbing resins and reducing the amount of hydrophilic fibre, if absorber absorbing fluid, increase the volume of absorber because of the swelling of water-absorbing resins, the shortcoming that this result can be brought between fiber or the winding of water-absorbing resins and fiber reduces.As between this fiber or the minimizing of the winding of water-absorbing resins and fiber, if give the distortion such as absorber compression or shear strength will break, skew, in addition, the backflow of liquid absorption or generation liquid can be hindered, therefore become the large shortcoming of the situation using water-absorbing body as hygienic material.
In the past, the method of being out of shape as preventing absorber, knownly by being mixed in paper pulp by meldable fibre, the adhesion strength between meldable fibre, between paper pulp and meldable fibre is achieved, thus improves the method (with reference to patent document 1) of the conformality of absorber.But in the method for patent document 1, the conformality of absorber is improved, but meldable fibre is lyophobic dust, therefore there is the shortcoming of liquid permeation rate or uptake decline.
With such prior art as a setting, when for absorber, wait in expectation and develop a kind of water-absorbing resins that can improve the conformality of absorber.
At first technical literature
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 63-92701 publication
Summary of the invention
Problem to be solved by this invention
The object of the present invention is to provide a kind of water absorbing properties excellent, at the water-absorbing resins of the conformality for absorber can be improved when absorber.In addition, another object of the present invention is to provide a kind of absorber and the absorbent commodity that utilize this water-absorbing resins.
For solving the scheme of problem
Present inventor has carried out deeply studying widely to solve aforementioned problems, found that, by water soluble alkene keyed unsaturated monomer, in hydrocarbon dispersant, in the water-absorbing resins that use radical polymerization initiator carries out inverse suspension polymerization and obtains, by meeting physiological saline water holding capacity, physiological saline water absorbing capacity under 4.14kPa load and swelling 50 times time gel tan δ in particular range, except the distortion of the absorber using water-absorbing resins can be suppressed, the seepage velocity of liquid is fast, and can suppress once the backflow of the liquid absorbed, thus obtain having excellent absorbent properties and the absorber of conformality concurrently.The present invention is found to be basis with above-mentioned just, and has carried out more deep research and complete.
That is, the invention provides following water-absorbing resins, absorber and absorbent commodity.
Item 1, a kind of water-absorbing resins, it is by water soluble alkene keyed unsaturated monomer in hydrocarbon dispersant, the water-absorbing resins that use radical polymerization initiator carries out inverse suspension polymerization and obtains,
It possesses the characteristic of following (1) ~ (3):
(1) physiological saline water holding capacity is more than 38g/g;
(2) the physiological saline water absorbing capacity under 4.14kPa load is more than 15mL/g;
(3) swelling 50 times time gel tan δ be 2.10 × 10 -2above.
2, the water-absorbing resins according to item 1, wherein, described water soluble alkene keyed unsaturated monomer for being selected from (methyl) acrylic acid and salt thereof, at least a kind in (methyl) acrylamide and N,N-DMAA.
3, the water-absorbing resins according to item 1 or 2, wherein, described water-absorbing resins is cross-linked by internal crosslinking agent and rear crosslinking agent.
4, the water-absorbing resins according to item 3, wherein, the use amount of internal crosslinking agent, relative to the water soluble alkene keyed unsaturated monomer 1 mole paying polymerization, is 0.000015 ~ 0.00020 mole,
The use amount of rear crosslinking agent, relative to the water soluble alkene keyed unsaturated monomer 1 mole paying polymerization, is 0.00025 ~ 0.0010 mole.
5, the water-absorbing resins according to item 3 or 4, wherein, internal crosslinking agent and rear crosslinking agent are multi-shrinking glyceryl compound.
6, a kind of absorber, it contains water-absorbing resins according to any one of item 1 ~ 5 and hydrophilic fibre.
7, a kind of absorbent commodity, it is formed between liquid permeability sheet material and liquid-impermeable sheet material for being remained on by the absorber described in item 6.
The manufacture method of item 8, a kind of water-absorbing resins, wherein,
Described water-absorbing resins possesses the characteristic of following (1) ~ (3),
(1) physiological saline water holding capacity is more than 38g/g;
(2) the physiological saline water absorbing capacity under 4.14kPa load is more than 15mL/g;
(3) swelling 50 times time gel tan δ be 2.10 × 10 -2above;
Further, the manufacture method of described water-absorbing resins comprises following first operation and the second operation:
First operation: in hydrocarbon dispersant, carries out the inverse suspension polymerization of water soluble alkene keyed unsaturated monomer under radical polymerization initiator and internal crosslinking agent exist;
Second operation: make it be cross-linked by rear crosslinking agent on the suspension polymerisation particle obtained in described first operation.
The manufacture method of the water-absorbing resins 9, according to item 8, wherein,
Described water soluble alkene keyed unsaturated monomer is be selected from least a kind in (methyl) acrylic acid and salt, (methyl) acrylamide and N,N-DMAA.
The manufacture method of the water-absorbing resins 10, according to item 8 or 9, wherein,
The use amount of the internal crosslinking agent in the first operation, relative to the water soluble alkene keyed unsaturated monomer 1 mole paying polymerization, is 0.000015 ~ 0.00020 mole;
The use amount of the rear crosslinking agent in the second operation, relative to the water soluble alkene keyed unsaturated monomer 1 mole paying polymerization, is 0.00025 ~ 0.0010 mole.
The manufacture method of the water-absorbing resins 11, according to any one of item 8 ~ 10, wherein,
Internal crosslinking agent and rear crosslinking agent are multi-shrinking glyceryl compound.
The effect of invention
Water-absorbing resins of the present invention by meet physiological saline water holding capacity, physiological saline water absorbing capacity under 4.14kPa load and swelling 50 times time gel tan δ at particular range, use the absorber of water-absorbing resins can possess excellent conformality, therefore when for hygienic material, even if give compression or shear strength due to the motion of wearer, also can the distortion of decrease uptake body, can prevent it from breaking, offseting simultaneously.In addition, water-absorbing resins of the present invention, by possessing above-mentioned characteristic, thus uses the absorber of water-absorbing resins also can possess excellent absorbent properties, and the seepage velocity of liquid is fast, and can suppress once the backflow of the liquid absorbed.
Like this, water-absorbing resins of the present invention possesses excellent water absorbing properties, can be used for absorber or the absorbent commodity of various uses.Particularly, water-absorbing resins of the present invention is preferred for the hygienic material of disposable diaper etc.
Accompanying drawing explanation
Fig. 1 is the structural representation of the device represented for measuring the physiological saline water absorbing capacity of water-absorbing resins under 4.14kPa load.
Fig. 2 is the top view of structural representation when representing the deformation time seeing mensuration absorbent commodity from above.
Detailed description of the invention
Water-absorbing resins of the present invention, for by water soluble alkene keyed unsaturated monomer in hydrocarbon dispersant, the water-absorbing resins that use radical polymerization initiator carries out inverse suspension polymerization and obtains, is characterized in that: the characteristic possessing following (1) ~ (3).
(1) physiological saline water holding capacity is more than 38g/g;
(2) the physiological saline water absorbing capacity under 4.14kPa load is more than 15mL/g;
(3) swelling 50 times time gel tan δ be 2.10 × 10 -2above.
Below, water-absorbing resins of the present invention is specifically described.
the characteristic of water-absorbing resins
(1) physiological saline water holding capacity
The physiological saline water holding capacity of water-absorbing resins of the present invention is more than 38g/g, is preferably more than 40g/g.For the higher limit of this physiological saline water holding capacity, be not particularly limited, such as, can enumerate below 60g/g, be preferably below 50g/g, be more preferably 47g/g.As this physiological saline water holding capacity, preferably enumerate 38 ~ 60g/g, be more preferably 40 ~ 50g/g, most preferably be 40 ~ 47g/g.It should be noted that, the physiological saline water holding capacity of water-absorbing resins is the numerical value that the assay method described in " physiological saline water holding capacity " described later measures.
(2) physiological saline water absorbing capacity under a load
The physiological saline water absorbing capacity of water-absorbing resins of the present invention under 4.14kPa load is more than 15mL/g, is preferably more than 18ml/g, is more preferably more than 21ml/g.For the higher limit of physiological saline water absorbing capacity under which loading, be not particularly limited, such as, can enumerate below 30mL/g, be preferably below 28mL/g, be more preferably below 25mL/g.As physiological saline water absorbing capacity under which loading, preferably enumerate 18 ~ 30mL/g, be more preferably 21 ~ 28mL/g, most preferably be 21 ~ 25mL/g.It should be noted that, the physiological saline water absorbing capacity of water-absorbing resins under 4.14kPa load refers to, the assay method described in " the physiological saline water absorbing capacity under 4.14kPa load " described later measures numerical value.
(3) viscoplasticity time swelling
Water-absorbing resins of the present invention, makes its swelling 50 times and the tan δ obtaining gel for 2.10 × 10 with physiological saline -2above, 2.15 × 10 are preferably -2above.For the higher limit of this tan δ, be not particularly limited, such as, can enumerate 2.80 × 10 -2below, 2.40 × 10 are preferably -2below.As this tan δ, preferably enumerate 2.10 × 10 -2~ 2.80 × 10 -2, be more preferably 2.15 × 10 -2~ 2.40 × 10 -2.
About the detailed description of tan δ, such as, in " high molecular viscoplasticity " (John D.FeRRy work, the wide prison in grandfather river is translated, and village allows the positive husband of Ji, high bridge translate altogether, the same people of Tokyo chemistry, and in October, 1964 issues) 28 ~ 34 pages described in.Usually in viscoelasticity evaluation, the model representation that macromolecular material is made up of elastic component and viscosity component.The former is for changing the composition of repulsion energy into by impact energy, the latter is composition impact energy being changed into dissipation energy.In the Measurement of Dynamic Viscoelasticity of being undertaken by vibration strains, be physically expressed as complex elastic-modulus G*=G '+iG " (i is imaginary unit).At this, G ' (storage elastic modulus) and G ' (loss elastic modulus) represents the elastic component of macromolecular material and the size of viscosity component separately.And, tan δ (Damage Shi Department number)=G " index of energy of/G ' for losing during material deformation.It should be noted that, the viscoplasticity (making the tan δ of its 50 times of swollen gel in physiological saline) when water-absorbing resins is swelling is the numerical value that the assay method described in " the tan δ of 50 times of swell gel " described later measures.
Water-absorbing resins of the present invention, by meeting the characteristic of above-mentioned (1) ~ (3), even if use the absorber of water-absorbing resins to apply compression or shear strength under the state of absorbing fluid, also can break or offset by decrease uptake body, stably keep the shape of absorber, possess excellent conformality.In addition, water-absorbing resins of the present invention is by meeting above-mentioned 3 characteristics, thus the absorber of use water-absorbing resins possesses excellent absorbent properties, and the absorptive capacity of liquid seepage velocity that is large, liquid is fast, the gel blocking phenomenon produced when absorbing fluid can be suppressed simultaneously, stably can keep absorbent properties.At this, " gel blocking phenomenon " refers to, when using the absorber of a large amount of water-absorbing resins, by being present in a large amount of water-absorbing resins absorbing fluid near top layer, the gel of the softness near top layer becomes more crypto set, thus hindering liquid to permeate to water-absorbing resins, water-absorbing resins becomes can not the phenomenon of absorbing fluid effectively.And then, water-absorbing resins of the present invention is by meeting the characteristic of above-mentioned (1) ~ (3), thus in the absorber using water-absorbing resins, can improve and keep, once the effect of the liquid absorbed, also can suppressing the backflow because of the caused liquid such as distortion or compression.
As the median particle diameter of water-absorbing resins of the present invention, be not particularly limited, such as, can enumerate 200 ~ 600 μm, be preferably 250 ~ 550 μm, be more preferably 300 ~ 500 μm.The median particle diameter of water-absorbing resins is the numerical value that the assay method described in " median particle diameter " described later measures.
the manufacture method of water-absorbing resins
Water-absorbing resins of the present invention be by by water soluble alkene keyed unsaturated monomer in hydrocarbon dispersant, use radical polymerization initiator to carry out inverse suspension polymerization, obtain in the scope crosslink density of suspension polymerisation particle being adjusted to defined.More specifically, water-absorbing resins of the present invention obtains by following first operation and the second operation.
First operation: in hydrocarbon dispersant, under the internal crosslinking agent of radical polymerization initiator and ormal weight exists, carries out inverse suspension polymerization by water soluble alkene keyed unsaturated monomer;
Second operation: make it be cross-linked by the rear crosslinking agent of ormal weight on the suspension polymerisation particle obtained in above-mentioned first operation.
Below, above-mentioned first operation and the second operation are described in detail.
< first operation >
In first operation, in hydrocarbon dispersant, under the existence of the internal crosslinking agent of radical polymerization initiator and ormal weight, by water soluble alkene keyed unsaturated monomer is carried out inverse suspension polymerization, thus obtain suspension polymerisation particle.
[water soluble alkene keyed unsaturated monomer]
For the water soluble alkene keyed unsaturated monomer used as raw material, be not particularly limited, such as, can enumerate (methyl) acrylic acid and (merge " propylene " and " metering system " in this description referred to as " (methyl) propylene ".Identical below), and salt; 2-(methyl) acrylamide-2-methyl propane sulfonic and salt thereof; The non-ionic monomer of (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, (methyl) acrylic acid 2-hydroxyl ethyl ester, N-methylol (methyl) acrylamide, polyethyleneglycol (methyl) acrylate etc.; N, the unsaturated monomer containing amino of N-diethyl amino ethyl group (methyl) acrylate, N, N-diethyl amino propyl (methyl) acrylate, diethyl amino propyl (methyl) acrylamide etc. and quaternary ammonium compound etc. thereof.These water soluble alkene keyed unsaturated monomers, can a kind be used alone, but also two or more combinationally uses.
In these water soluble alkene keyed unsaturated monomers, preferably enumerate (methyl) acrylic acid and salt thereof, (methyl) acrylamide, N,N-DMAA; Be more preferably (methyl) acrylic acid and salt, acrylamide.
Water soluble alkene keyed unsaturated monomer, when inverse suspension polymerization, in order to make the dispersion efficiency in hydrocarbon dispersant rise, can use the aqueous solution.The concentration of the above-mentioned monomer in this aqueous solution is not particularly limited, and is usually located at below the above saturated concentration of 20 quality %, preferably enumerates 25 ~ 70 quality %, be more preferably 30 ~ 55 quality %.
Water soluble alkene keyed unsaturated monomer, when (methyl) acrylic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic etc. such there is acidic group, by antalkali, this acidic group is neutralized.As this antalkali, NaOH, potassium hydroxide, ammonia etc. can be used.These antalkalis can a kind be used alone, but also two or more combinationally uses.
By the degree of neutralization in whole acidic groups of water soluble alkene keyed unsaturated monomer of antalkali, to pass through the osmotic pressure of the water-absorbing resins that raising obtains thus to improve water absorbing capacity, and the existence of remaining antalkali can not cause the mode that problem occurs in security etc. to carry out setting, such as can enumerate 10 ~ 100 % by mole, be preferably 30 ~ 80 % by mole.
[hydrocarbon dispersant]
As long as hydrocarbon dispersant is the hydrocarbon that can be used as dispersant use in the inverse suspension polymerization of water soluble alkene keyed unsaturated monomer, just be not particularly limited, such as can enumerate the aliphatic hydrocarbon of n-hexane, normal heptane, 2-methyl hexane, 3-methyl hexane, 2,3-dimethyl pentanes, 3-hexyl pentane, normal octane etc.; Cyclohexane, hexahydrotoluene, pentamethylene, methyl cyclopentane, anti-form-1,2-dimethylcyclopentane, cis-1,3-dimethylcyclopentane, anti-form-1, the clicyclic hydrocarbon of 3-dimethylcyclopentane etc.; The aromatic hydrocarbon etc. of benzene,toluene,xylene etc.In these hydrocarbon dispersants, from industrially easily obtaining, steady quality and low-cost viewpoint, preferably enumerate n-hexane, normal heptane and cyclohexane.These hydrocarbon dispersants can a kind be used alone, but also two or more combinationally uses.As the suitable example of the mixture of above-mentioned hydrocarbon dispersant, commercially available Exxsol Heptance (Ke Sen Mobil society system: the hydrocarbon containing 75 ~ 85 quality % heptane and isomers) etc. can be enumerated.
The use amount of hydrocarbon dispersant, from the viewpoint of easily removing heat of polymerization, controlling polymerization temperature, relative to water soluble alkene keyed unsaturated monomer 100 mass parts, usually can enumerate 50 ~ 600 mass parts, be preferably 80 ~ 550 mass parts.
[radical polymerization initiator]
For radical polymerization initiator, such as, can enumerate the persulfuric acid salt of potassium peroxydisulfate, ammonium persulfate and sodium peroxydisulfate etc., the peroxide of methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-tert-butyl peroxide, t-butylcumylperoxide, peroxide acetic acid butyl ester, peroxidating tert-butyl isobutyrate, tert-Butyl peroxypivalate and hydrogen peroxide etc., 2, two (2-amidine propane) dihydrochloride of 2 '-azo, 2, two [2-(the N-phenyl amidino groups) propane] dihydrochloride of 2 '-azo, 2, two [2-(the N-pi-allyl amidino groups) propane] dihydrochloride of 2 '-azo, 2, two { 2-[1-(2-the hydroxyethyl)-2-imidazoline-2-base] propane } dihydrochloride of 2 '-azo, 2, two { 2-methyl-the N-[1 of 2 '-azo, two (the hydroxymethyl)-2-hydroxyethyl of 1-] propionamide }, 2, 2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionamide], and 4, the azo-compound etc. of 4 '-azo two (4-cyanopentanoic acid) etc.In these radical polymerization initiators, from the viewpoint of easily to obtain and easy to operate, preferably enumerate potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate and 2, two (2-amidine propane) dihydrochloride of 2 '-azo.These radical polymerization initiators can a kind be used alone, but also two or more combinationally uses.
In addition, above-mentioned radical polymerization initiator with the reducing agent of sodium sulfite, sodium hydrogensulfite, ferrous sulfate and L-AA etc. and use, also can be used as redox polymerization initator and uses.
For the use amount of radical polymerization initiator, be not particularly limited, such as can enumerate relative to water soluble alkene keyed unsaturated monomer 1 mole is 0.00005 ~ 0.01 mole.By meeting this use amount, the generation of polymerisation rapidly can be avoided, and polymerisation can be made to complete at reasonable time.
[internal crosslinking agent]
Internal crosslinking agent for give suspension polymerisation particle appropriateness crosslink density, make the water-absorbing resins finally obtained possess excellent water absorbing properties.
For the kind of internal crosslinking agent, as long as crosslinkable suspension polymerisation particle, be not particularly limited, (" (gathering) " refers to and does not have the situation of " gathering " prefix such as can to enumerate (gathering) ethylene glycol.Identical below), (gathering) propane diols, BDO, trihydroxymethyl propane, the polyalcohols of dihydroxylic alcohols, trihydroxylic alcohol etc. of (gathering) glycerine etc. and the unsaturated acids reaction of (methyl) acrylic acid, maleic acid, fumaric acid etc. and the unsaturated polyester (UP) class that obtains; The bisacrylamide class of N, N-methylene-bisacrylamide etc.; Polyepoxide and (methyl) acrylic acid are reacted and two (methyl) esters of acrylic acids that obtain or three (methyl) esters of acrylic acid; The polyisocyanates of inferior cresyl vulcabond, hexamethylene diisocyanate etc. and (methyl) hydroxy-ethyl acrylate are reacted and two (methyl) acrylic-amino carbamoyl ester class of obtaining; Allyl starch, allylation cellulose, diallyl phthalate, N, N ', N " compound with more than 2 polymerism unsaturated groups of-triallyl isocyanate, divinylbenzene etc.; The multi-shrinking glyceryl compound of the multi-shrinking glyceryl compound, triglycidyl group compound etc. of (gathering) ethylene glycol diglycidylether, (gathering) propylene glycol diglycidylether, (gathering) glycerin diglycidyl ether etc.; The epoxyhalopropane compound of epoxychloropropane, epoxy bromopropane, Alpha-Methyl epoxychloropropane etc.; The compound with more than 2 reactive functional groups of the isocyanate compound of 2,4-toluene di-isocyanate(TDI), hexamethylene diisocyanate etc. etc.; The oxetane compound etc. of 3-methyl-3-hydroxymethyl-oxetane, 3-ethyl-3-hydroxymethyl-oxetane, 3-butyl-3-hydroxymethyl-oxetane, 3-methyl-3-ethoxy oxetanes, 3-ethyl-3-ethoxy oxetanes, 3-butyl-3-ethoxy oxetanes etc.Preferably enumerate multi-shrinking glyceryl compound in these internal crosslinking agents, be more preferably 2-glycidyl ether compound, be more preferably (gathering) ethylene glycol diglycidylether.These internal crosslinking agents can a kind be used alone, but also two or more combinationally uses.
The use amount of internal crosslinking agent, for the water soluble alkene keyed unsaturated monomer 1 mole paying polymerization, is set as 0.000015 ~ 0.00020 mole, preferably enumerates 0.000020 ~ 0.000150 mole, be more preferably 0.000030 ~ 0.000080 mole.By using internal crosslinking agent in this scope, the water-absorbing resins finally obtained can be made to possess excellent water absorbing properties.
[dispersion stabilizer]
The inverse suspension polymerization carried out in above-mentioned first operation, is separated into object with stable water soluble ethylenically unsaturated monomers, can use dispersion stabilizer as required.For dispersion stabilizer, such as, surfactant can be enumerated.For the surfactant that dispersion stabilizer uses, specifically can exemplify the nonionic system surfactant of sorbitan fatty acid ester, polyglyceryl fatty acid ester, sucrose fatty ester, Span, polyoxyethylene alkyl phenyl ether etc.; The anion system surfactant etc. of soap, alkylbenzenesulfonate, alkyl methyl taurine salt, polyoxyethylene alkyl phenyl ether sulfuric acid, polyoxyethylene alkyl ether sulfonate etc.In these surfactants, from the viewpoint of the dispersion stabilization of water soluble alkene keyed unsaturated monomer, preferably enumerate sorbitan fatty acid ester, polyglyceryl fatty acid ester and sucrose fatty ester.These surfactants can a kind be used alone, but also two or more combinationally uses.
The use amount of surfactant, well can keep the dispersity of the water soluble alkene keyed unsaturated monomer in hydrocarbon dispersant, and set aptly in the scope that can obtain the dispersion effect conformed to use amount, such as can enumerate relative to water soluble alkene keyed unsaturated monomer 100 mass parts is 0.1 ~ 5 mass parts, is preferably 0.2 ~ 3 mass parts.
In addition, as dispersion stabilizer, surfactant and macromolecule dispersing agent can be used.As the macromolecule dispersing agent used, such as, can enumerate ethyl cellulose, ethylhydroxyethylcellulose, polyoxyethylene, maleated polyethylenes, maleic anhydride modified ethylene propylene copolymer, maleation polybutadiene, maleation EPDM (Ethylene-Propylene-Diene-terpolymer) etc.
The use amount of macromolecule dispersing agent, the dispersity of the water soluble alkene keyed unsaturated monomer in hydrocarbon dispersant can kept well, and set aptly in the scope that can obtain the dispersion effect conformed to use amount, such as can enumerate relative to water soluble alkene keyed unsaturated monomer 100 mass parts is 0.1 ~ 5 mass parts, is preferably 0.2 ~ 3 mass parts.
In addition, as dispersion stabilizer, thickener can be used.For the thickener used as dispersion stabilizer, such as, can enumerate hydroxyethylcellulose, hydroxypropyl cellulose, methylcellulose, carboxymethyl cellulose, polyacrylic acid, polyacrylic acid (part) corrective, polyethylene glycol, polyacrylamide, polymine, dextrin, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol oxide etc.
[condition of inverse suspension polymerization reaction]
Inverse suspension polymerization in above-mentioned first operation, be by the water soluble alkene keyed unsaturated monomer of interpolation ormal weight, radical polymerization initiator, internal crosslinking agent and dispersion stabilizer as required in hydrocarbon dispersant, heating, carries out.
The reaction temperature of inverse suspension polymerization reaction, different according to the kind of radical polymerization initiator used, can not determine without exception, usually can enumerate 20 ~ 110 DEG C, preferably 40 ~ 80 DEG C.By setting this reaction temperature, polymerization time can be suppressed elongated, also can remove heat of polymerization simultaneously and carrying out with making stable polymerization reaction.
For the reaction time of inverse suspension polymerization reaction, consider that the kind, amount, reaction temperature etc. of the starting compound used set aptly, usually can enumerate 0.5 ~ 4 hour.
Inverse suspension polymerization reaction in above-mentioned first operation can be carried out in 1 stage, also carried out with the multistages more than 2 stages.This number of stages is considered from the productive viewpoint of raising, preferably enumerates 2 stages or 3 stages.
When the inverse suspension polymerization reaction carrying out 2 stages more than, carry out the inverse suspension polymerization in 1 stage by above-mentioned method after, add water soluble alkene keyed unsaturated monomer in the reactant mixture obtained in the polymerisation in 1 stage and mix, the inverse suspension polymerization undertaken after 2 stages by the method identical with 1 stage is reacted.In inverse suspension polymerization in each stage after 2 stages, except water soluble alkene keyed unsaturated monomer, using the amount of the water soluble alkene keyed unsaturated monomer added during the inverse suspension polymerization in each stage after 2 stages as benchmark, in the scope of the mol ratio of each composition relative to above-mentioned water soluble alkene keyed unsaturated monomer, add radical polymerization initiator, internal crosslinking agent etc., carry out inverse suspension polymerization by the condition identical with said method and react.
< second operation >
In second operation, the suspension polymerisation particle obtained in above-mentioned first operation carries out rear crosslinking Treatment by rear crosslinking agent.Like this, suspension polymerisation particle carries out rear crosslinking Treatment by rear crosslinking agent, implements the crosslinked of appropriateness in above-mentioned first operation in the suspension polymerisation particle obtained, and water-absorbing resins can be made to possess excellent water absorbing properties.
As long as rear crosslinking agent can react with the functional group of water-absorbing resins (such as carboxyl), just be not particularly limited, such as can enumerate the polyalcohols of (gathering) ethylene glycol, (gathering) propane diols, BDO, trihydroxymethyl propane, (gathering) glycerine etc., (gathering) ethylene glycol diglycidylether, (gathering) propylene glycol diglycidylether, the diglycidyl compounds of (gathering) glycerin diglycidyl ether etc., (gathering) ethylene glycol three-glycidyl ether-ether, (gathering) propane diols three-glycidyl ether-ether, the triglycidyl group compound of (gathering) glycerin triglycidyl ether ester etc., (gathering) propane diols polyglycidyl ether, the multi-shrinking glyceryl compound of the glycidyl compound of more than 3 yuan of (gathering) glycerol polyglycidylether etc. etc., epoxychloropropane, epoxy bromopropane, αthe halogen epoxide of-methyl epichlorohydrin etc., the compound with the reactive functional groups of more than 2 of the isocyanate compound of 2,4-toluene di-isocyanate(TDI), hexamethylene diisocyanate etc. etc., the oxetane compound of 3-methyl-3-hydroxymethyl-oxetane, 3-ethyl-3-hydroxymethyl-oxetane, 3-butyl-3-hydroxymethyl-oxetane, 3-methyl-3-ethoxy oxetanes, 3-ethyl-3-ethoxy oxetanes, 3-butyl-3-ethoxy oxetanes etc., the oxazoline compounds such as 1,2-Ya Jia Ji bisoxazoline, the carbonate products etc. of ethylene carbonate etc.In crosslinking agent after these, preferably enumerate multi-shrinking glyceryl compound, be more preferably diglycidyl compounds, most preferably be (gathering) ethylene glycol diglycidyl base ether.After these crosslinking agents can a kind be used alone, but also two or more combinationally uses.
The use amount of rear crosslinking agent, relative to the total amount 1 mole of the water soluble alkene keyed unsaturated monomer used in the inverse suspension polymerization reaction of above-mentioned first operation, be set as 0.00025 ~ 0.0010 mole, preferably enumerate 0.00044 ~ 0.00080 mole, be more preferably 0.00044 ~ 0.00076 mole.By using rear crosslinking agent in this scope, the suspension polymerisation particle obtained in above-mentioned first operation can be made to possess the crosslink density of appropriateness, for the water-absorbing resins finally obtained, the water absorbing properties of its excellence can be given.
As long as interpolation period of rear crosslinking agent is after above-mentioned first operation terminates, be not particularly limited.After adding during crosslinking agent, relative to total amount 100 mass parts in order to obtain the water soluble alkene keyed unsaturated monomer that water-absorbing resins uses, be preferably and add under the moisture of the scope of 1 ~ 400 mass parts exists, be more preferably and add under the moisture of the scope of 5 ~ 200 mass parts exists, most preferably be and add under the moisture of the scope of 10 ~ 100 mass parts exists.
After adding during crosslinking agent, the solvent of water or hydrophilic organic solvent etc. can be used.For the hydrophilic organic solvent used as rear crosslinking Treatment solvent, such as, can enumerate the lower alcohols of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol etc.; The ketone of acetone, methyl ethyl ketone etc.; The ethers of ether, dioxane, oxolane etc.; The sulfoxide type etc. of the amide-type, methyl-sulfoxide etc. of DMF etc.These hydrophilic organic solvents can a kind be used alone, but also two or more combinationally uses.In addition, for the solvent of rear crosslinking Treatment, the independent one of water or hydrophilic organic solvent can be used, also can use the mixed solvent of water and hydrophilic organic solvent.
The reaction temperature of rear crosslinking Treatment, is not particularly limited, such as, can enumerate 50 ~ 250 DEG C, is preferably 60 ~ 180 DEG C, is more preferably 60 ~ 140 DEG C, most preferably is 70 ~ 120 DEG C.
In addition, the reaction time of rear crosslinking Treatment, different according to the kind of reaction temperature, rear crosslinking agent and use amount etc., can not determine without exception, usually can enumerate 1 ~ 300 minute, be preferably 5 ~ 200 minutes.
Like this, by carrying out the first operation and the second operation, thus produce and possess excellent water absorbing properties and at the water-absorbing resins of the conformality for absorber can be improved during absorber.
In recovery water-absorbing resins after the second operation, hydrocarbon dispersant or solvent are removed.For the method except dealkylation dispersant or solvent, be not particularly limited, such as, can enumerate dry process.Dry process can be carried out at ambient pressure, also can under reduced pressure carry out.In addition, in order to improve drying efficiency, also drying process can be carried out under the air-flow of nitrogen etc.In addition, at ambient pressure in withering situation, as baking temperature, such as, can enumerate 70 ~ 250 DEG C, be preferably 80 ~ 180 DEG C, be more preferably 80 ~ 140 DEG C, most preferably be 90 ~ 130 DEG C.In addition, under reduced pressure in withering situation, as baking temperature, such as, can enumerate 60 ~ 100 DEG C, be preferably 70 ~ 90 DEG C.
absorber and absorbent commodity
Absorber of the present invention is made up of above-mentioned water-absorbing resins of the present invention and hydrophilic fibre.For the formation of this absorber, be not particularly limited, such as can enumerate the mixed structure that water-absorbing resins and hydrophilic fibre are mixed equably, the sandwich keeping water-absorbing resins between the hydrophilic fibre of stratiform, water-absorbing resins and hydrophilic fibre are wrapped up with the wrapping paper of thin paper etc. after structure etc.
As hydrophilic fibre, be not particularly limited, such as, can enumerate the cellulose fibre of the cotton like paper pulp, mechanical pulp, chemical pulp, semichemical wood pulp etc. obtained by timber; The artificial fiber cellulose fiber of artificial cellosilk, acetate silk etc.; The fiber etc. that the synthetic resin of the polyamide after hydrophilicity-imparting treatment, polyester, polyolefin etc. is formed.
And then, in absorber of the present invention, except above-mentioned water-absorbing resins and hydrophilic fibre, the cementability adhesive of the hot melt property synthetic fibers, hot-melt adhesive, cementability emulsion etc. of the conformality improving absorber can be added to as required.
The content of the water-absorbing resins in absorber of the present invention, is not particularly limited, such as, can enumerate 30 ~ 85 quality %, is preferably 40 ~ 80 quality %, is more preferably 45 ~ 70 quality %.Water-absorbing resins, by meeting above-mentioned content, makes the liquid absorption quantitative change of absorber many, can suppress leakage or the backflow of liquid, and can obtain good use sense.
In addition, by being remained on by above-mentioned absorber of the present invention between liquid permeability sheet material (top-sheet) that liquid can pass through and the liquid-impermeable sheet material (back sheet material) that liquid can not pass through, thus can be used as absorbent commodity.Liquid permeability sheet material is configured in the side with Body contact, and liquid-impermeable sheet material is configured in the opposite side with Body contact.
For liquid permeability sheet material, such as, can enumerate the nonwoven fabric and cavernous synthetic resin sheet material etc. of the ventilation type, spunbonded type, chemical adhesion type, needle-penetrating etc. be made up of the fiber of polyethylene, polypropylene, polyester etc.
For liquid-impermeable sheet material, such as, can enumerate the film of synthetic resin etc. formed by the resin of polyethylene, polypropylene, polyvinyl chloride etc.
For the kind of absorbent commodity, be not particularly limited, such as, can enumerate the hygienic material of paper nappy, sanitary napkin, incontinence protection etc.; The urine absorbing material of pet; The civil construction goods, materials and equipments of packaging material etc.; The maintenance food freshness material of dropping liquid absorbent, cold-producing medium etc.; The soil Reel agronomy article etc. of water conservation material etc.In the middle of these, due to hygienic material be with the state of human contact under use, therefore need that there is excellent use sense (fast liquid permeation rate and few liquid back amount), simultaneously for the compression of institute's load when wearing or the patience (conformality) of shear strength, absorbent commodity of the present invention is especially suitable.
Embodiment
Below, describe the present invention based on embodiment and comparative example, but the present invention is not by the restriction of embodiment.
For the water-absorbing resins obtained in each embodiment and comparative example, by tan8 and the median particle diameter of method as follows mensuration physiological saline water holding capacity, the physiological saline water absorbing capacity under 4.14kPa load, 50 times of swell gel.
< physiological saline water holding capacity >
In the beaker of 500mL capacity, measure 0.9 quality % sodium-chloride water solution (physiological saline) 500g, with 600 revs/min of stirrings, while make water-absorbing resins 2.0g not disperse with not producing caking.Place 30 minutes under the state stirred, make water-absorbing resins swelling fully.Then, be poured into cotton bag (cotton No. 60, wide (メ Application Block mouth one De), horizontal 100mm × vertical 200mm) in, the top rubber band of cotton bag is tied, centrifugal force is used to be set to dewaterer (domestic centrifuge Co., Ltd. system of 167G, production code member: H-122), cotton bag is dewatered 1 minute, measure the quality Wa (g) of the cotton bag containing swell gel after dehydration.Do not add water-absorbing resins and carry out identical operation, measure the empty quality Wb (g) during cotton bag moistening, go out water holding capacity by following formulae discovery.
The quality (g) of physiological saline water holding capacity (g/g)=[Wa-Wb] (g)/water-absorbing resins
The physiological saline water absorbing capacity > of < under 4.14kPa load
The physiological saline water absorbing capacity under 4.14kPa load of water-absorbing resins, measures by using the determinator X of structural signal in FIG.
Determinator X in FIG by buret portion 1 and conduit 2, measure platform 3 and be placed on the determination part 4 measured on platform 3 and form.Buret portion 1 is connected with rubber bolt 14 on the top of buret 10, bottom is connected with air leading-in conduit 11 and cock 12, and then cock 13 is arranged at the top of air leading-in conduit 11.From buret portion 1 to mensuration platform 3, be provided with conduit 2, the diameter of conduit 2 is 6mm.Measuring the central portion of platform 3, have the hole that diameter is 2mm, connecting duct 2.Determination part 4 has cylinder 40, is attached at nylon wire 41 and the plummet 42 of the bottom of this cylinder 40.The internal diameter of cylinder 40 is 2.0cm.And, the nylon wire 41 in 200 meshes (75 μm, aperture) is studded with the water-absorbing resins 5 of ormal weight equably.Plummet 42 diameter is 1.9cm, and quality is 119.6g.This plummet 42 is arranged on water-absorbing resins 5, can apply the load of 4.14kPa relative to water-absorbing resins 5 equably.
In the determinator X so formed, first close cock 12 and the cock 13 in buret portion 1, the physiological saline being adjusted to 25 DEG C is added from buret 10 top, seals buret top by rubber bolt 14, open the cock 12 in buret portion 1, cock 13.Then, carry out in the mode identical with the height of the air induction port of air leading-in conduit 11 on the top of the conduit 2 measuring platform 3 central part the adjustment measuring platform 3 height.
On the other hand, the nylon wire 41 of cylinder 40 scatters the water-absorbing resins 5 of 0.10g equably, place plummet 42 by this water-absorbing resins 5.Determination part 4 is set, to make its central part consistent with the conduit mouth measuring platform 3 central part.
From water-absorbing resins 5, the time point of water suction starts reduction (saline volume that the water-absorbing resins 5 absorbs) Wc (mL) of the physiological saline read constantly in buret 10.The physiological saline water absorbing capacity of water-absorbing resins 5 under 4.14kPa load from water suction after 60 minutes, is calculated by following formula.
Physiological saline water absorbing capacity (mL/g) under 4.14kPa load=Wc (mL) ÷ 0.10 (g)
The tan δ > of <50 times of swell gel
In physiological saline, make the gel (50 times of swell gel) of swelling 50 times of water-absorbing resins, made by following method.In the beaker of 100mL capacity, measure physiological saline 49.0g, input magnetic stirring bar ( acyclic), be placed on magnetic stirring apparatus (Iuchi society system: HS-30D), adjustment magnetic stirring bar rotate in the mode of 600 revs/min.Then, water-absorbing resins 1.0g is dropped in the beaker in stirring, to disappear and liquid level stirs till becoming level until whirlpool always, thus prepared the gel of swelling 50 times.These 50 times of swell gel are moved to centrifuge tube, is set at centrifugal force carry out degassed, as working sample with 4 minutes in the centrifuge (domestic centrifuge Co., Ltd. system, production code member H-103NASERIES) of 671G.
Measure and then use Measurement of Dynamic Viscoelasticity device flow graph (TA instrument Amada Co., Ltd. (TAInstruments Japan Inc.) system, production code member AR2000eZ), measure storage elastic modulus G ' (Pa) and loss elastic modulus G " (Pa) frequencies omega (rad/ second) dispersion.Specimen holder uses the flat board that diameter is 60mm, and the distance between plate is set to 3mm.Measure temperature and be set to 25 ± 2 DEG C, in the scope of frequencies omega=0.1 ~ 300rad/ second, measure G ', G ", from G ' and G " ratiometer calculate the numerical value of the tan δ when 10rad/ second, using the tan δ of this numerical value as 50 times of swell gel of water-absorbing resins.
< median particle diameter >
The amorphous silica 0.25g (Degussa Japan (strain), SiPeRnat200) as lubricant is mixed in water-absorbing resins 50g.
Aperture is used to be that the JIS standard screen of 250 μm is by this mixture, when sieving the situation of upper residual its 50 quality % of quantity not sufficient, use the combination of the sieve of <A>, when the situation of more than 50 quality %, use the combination of the sieve of <B>, determine median particle diameter.
<A> is by JIS standard screen with from above, and the sieve that the sieve that the sieve that the sieve that the sieve that the sieve that aperture is 425 μm, aperture are 250 μm, aperture are 180 μm, aperture are 150 μm, aperture are 106 μm, aperture are 75 μm, aperture are the sieve of 45 μm and the sequential combination of disc.
<B> is by JIS standard screen with from above, and the sieve that the sieve that the sieve that the sieve that the sieve that the sieve that aperture is 850 μm, aperture are 600 μm, aperture are 500 μm, aperture are 425 μm, aperture are 300 μm, aperture are 250 μm, aperture are the sieve of 150 μm and the sequential combination of disc.
After combining on uppermost sieve, add above-mentioned water-absorbing resins, use Luo Taipu (Ro-Tap) formula vibrator to make it vibrate 20 minutes and carry out classification.
After classification, the quality of water-absorbing resins residual on each sieve is calculated as the mass percent relative to total amount, by integrating successively from particle diameter is large, by the relation drafting pattern between the accumulated value of the mass percent of water-absorbing resins residual on the aperture of sieve and sieve on logarithmic probability paper.By connecting with straight line probability paper painting a little, will the particle diameter of integrating mass percent 50 quality % be equivalent to as median particle diameter.
[embodiment 1]
Prepare to be furnished with reflux cooler, dropping funel, nitrogen ingress pipe, there is as agitator the detachable flask of round-ended cylinder type of the internal diameter 100mm of the agitator of 4 slurry wings that tilt of two-layer wing footpath 50mm.Normal heptane 500ml is got in this flask, add sucrose stearate (Mitsubishi Chemical's food (strain) system of HLB3, Ryoto Sugar Ester S-370) 0.80g, maleic anhydride modified ethylene/propene copolymer (Mitsui Chemicals (strain) make, HI-WAX1105A) 0.80g, be warming up to 80 DEG C and dissolve surfactant, being cooled to 50 DEG C afterwards.
The another acrylic acid aqueous solution 92g (1.02 moles) getting 80 quality % in the conical flask of 500ml, while external refrigeration, drip the sodium hydrate aqueous solution 153.2g of 20 quality % and carry out the neutralization of 75 % by mole, afterwards, add as thickener hydroxyethylcellulose 0.28g (refine in Sumitomo (strain) system, HEC AW-15F), as the potassium peroxydisulfate 0.07g (0.000259 mole) of radical polymerization initiator, as internal crosslinking agent ethylene glycol diglycidylether 0.011g (0.0000631 mole) and dissolve, prepare the monomer solution in the 1st stage.
The monomer solution in above-mentioned 1st stage is added in above-mentioned detachable flask, by in system while with nitrogen displacement, with 35 DEG C maintenances 30 minutes, afterwards, make it carry out polymerisation by flooding in the water-bath of 70 DEG C and heating up, thus obtain the polymerization disposed slurry in the 1st stage.
In addition, the acrylic acid aqueous solution 128.8g (1.43 moles) of 80 quality % is got in the conical flask of another 500mL capacity, while external refrigeration, drip the sodium hydrate aqueous solution 158.9g of 27 quality % and carry out the neutralization of 75 % by mole, afterwards, add the potassium peroxydisulfate 0.10g (0.000370 mole) as radical polymerization initiator, the ethylene glycol diglycidylether 0.013g (0.0000746 mole) as internal crosslinking agent and dissolve, having prepared the monomer solution in the 2nd stage.
Above-mentioned polymerization disposed slurry is cooled to 25 DEG C, the monomer solution in above-mentioned 2nd stage is added in system, use Dan Qi Zhi Change to keep 30 minutes.Again carry out polymerisation by heating up in the water-bath that flask be impregnated in 70 DEG C, thus obtain the polymerization disposed slurry in the 2nd stage.
Secondly, the oil bath of 125 DEG C is used to heat up, by azeotropic distillation water and normal heptane, the normal heptane while reflux, extracts the water of 270.1g out, afterwards outside system, add the ethylene glycol diglycidylether aqueous solution 9.94g (0.00114 mole) as 2 quality % of rear crosslinking agent, after keeping 2 hours at 80 DEG C, make it dry by evaporation normal heptane, thus obtain water-absorbing resins 231.2g.The measurement result of each performance is as shown in table 1.
[embodiment 2]
Except in embodiment 1, the water yield of extracting out during azeotropic distillation changes to 271.6g, the ethylene glycol diglycidylether aqueous solution as 2% quality of rear crosslinking agent changes to 11.04g (0.00126 mole), in addition carry out identical operation with embodiment 1, obtain water-absorbing resins 228.7g.The measurement result of each performance is as shown in table 1.
[embodiment 3]
Except in embodiment 1, the water yield of extracting out during azeotropic distillation changes to 273.8g, the ethylene glycol diglycidylether aqueous solution of 2% quality as rear crosslinking agent is changed to 13.25g (0.00152 mole), in addition carry out identical operation with embodiment 1, obtain water-absorbing resins 227.4g.The measurement result of each performance is as shown in table 1.
[embodiment 4]
Except in embodiment 1, chilling temperature before the monomer solution in interpolation the 2nd stage is changed to 23 DEG C, the water yield of extracting out during azeotropic distillation changes to 274.4g, the ethylene glycol diglycidylether aqueous solution of 2% quality as rear crosslinking agent is changed to 13.25g (0.00152 mole), in addition carry out identical operation with embodiment 1, obtain water-absorbing resins 228.2g.The measurement result of each performance is as shown in table 1.
[embodiment 5]
Prepare to be furnished with reflux cooler, the detachable flask of round-ended cylinder type that dropping funel, nitrogen ingress pipe, the internal diameter as agitator with the agitator of 4 slurry wings that tilt of two-layer wing footpath 50mm are 100mm.In this flask, get normal heptane 500ml, add sucrose hard acid ester (Mitsubishi Chemical's food (strain) is made, the Ryoto Sugar Ester S-370) 0.80g of HLB3, be warming up to 80 DEG C and dissolve surfactant, being cooled to 50 DEG C afterwards.
The another acrylic acid aqueous solution 92g (1.02 moles) getting 80 quality % in 500ml conical flask, while external refrigeration, drip the sodium hydrate aqueous solution 153.2g of 20 quality % and carry out the neutralization of 75 % by mole, afterwards, add as thickener hydroxyethylcellulose 0.28g (refine in Sumitomo (strain) system, HEC AW-15F), as 2 of radical polymerization initiator, two (2-amidine propane) the dihydrochloride 0.05g (0.000184 mole) of 2 '-azo, as internal crosslinking agent ethylene glycol diglycidylether 0.006g (0.0000344 mole) and dissolve, prepare the monomer solution in the 1st stage.
The monomer solution in above-mentioned 1st stage is made an addition in above-mentioned detachable flask, replaces in system with nitrogen, while keep 30 minutes with 35 DEG C, afterwards, flooding in the water-bath of 70 DEG C and heat up, by being polymerized, obtaining the polymerization disposed slurry in the 1st stage.
In addition, the acrylic acid aqueous solution 128.8g (1.43 moles) of 80 quality % is got in the conical flask of another 500mL capacity, while external refrigeration, drip the sodium hydrate aqueous solution 158.9g of 27 quality % and carry out the neutralization of 75 % by mole, afterwards, add 2 as radical polymerization initiator, two (2-amidine propane) the dihydrochloride 0.07g (0.000258 mole) of 2 '-azo, as internal crosslinking agent ethylene glycol diglycidylether 0.008g (0.0000459 mole) and dissolve, prepared the monomer solution in the 2nd stage.
Above-mentioned polymerization disposed slurry is cooled to 25 DEG C, the monomer solution in above-mentioned 2nd stage is added in the decorum, use Dan Qi Zhi Change to keep 30 minutes.Again carry out polymerisation by heating up in the water-bath that flask be impregnated in 70 DEG C, thus obtain the polymerization disposed slurry in the 2nd stage.
Secondly, the oil bath of 125 DEG C is used to heat up, by azeotropic distillation water and normal heptane, the normal heptane while reflux, extracts the water of 284.8g out, afterwards outside system, add the ethylene glycol diglycidylether aqueous solution 8.11g (0.00186 mole) as 4 quality % of rear crosslinking agent, after keeping 2 hours with 80 DEG C, make it dry by evaporation normal heptane, thus obtain water-absorbing resins 228.5g.The measurement result of each performance is as shown in table 1.
[comparative example 1]
Except in embodiment 1, the water yield of extracting out during azeotropic distillation changes to 260.2g, the ethylene glycol diglycidylether aqueous solution of 2% quality as rear crosslinking agent is changed to 4.48g (0.000514 mole), in addition carry out identical operation with embodiment 1, obtain water-absorbing resins 231.2g.The measurement result of each performance is as shown in table 1.
[comparative example 2]
Except in embodiment 1, the ethylene glycol diglycidylether added in the monomer solution in the 1st stage and the 2nd stage changes to 0.038g (0.000218 mole), 0.053g (0.000304 mole) respectively, the water yield of extracting out during azeotropic changes to 284.8g, in addition carry out identical operation with embodiment 1, obtain water-absorbing resins 228.4g.The measurement result of each performance is as shown in table 1.
[comparative example 3]
Except in embodiment 1, the ethylene glycol diglycidylether added in the monomer solution in the 1st stage and the 2nd stage changes to 0.008g (0.0000459 mole), 0.011g (0.0000631 mole) respectively, the ethylene glycol diglycidylether aqueous solution of 2% quality as rear crosslinking agent is changed to 4.91g (0.000563 mole), the water yield of extracting out during azeotropic changes to 272.3g, in addition carry out identical operation with embodiment 1, obtain water-absorbing resins 229.6g.The measurement result of each performance is as shown in table 1.
[comparative example 4]
Except in embodiment 1, the ethylene glycol diglycidylether added in the monomer solution in the 1st stage and the 2nd stage changes to 0.002g (0.0000114 mole), 0.003g (0.0000172 mole) respectively, in addition carry out identical operation with embodiment 1, obtain water-absorbing resins 228.7g.The measurement result of each performance is as shown in table 1.
[comparative example 5]
In embodiment 1, chilling temperature before the monomer solution in interpolation the 2nd stage is changed to 26 DEG C, the water yield of extracting out during azeotropic distillation changes to 286.3g, the ethylene glycol diglycidylether aqueous solution as 4% quality of rear crosslinking agent changes to 11.76g (0.00270 mole), in addition carry out identical operation with embodiment 1, obtain water-absorbing resins 229.8g.The measurement result of each performance is as shown in table 1.
Be used in the water-absorbing resins obtained in each embodiment and each comparative example, make absorber and absorbent commodity, by following method, liquid permeation rate, liquid back amount, conformality (deformation time) are evaluated.This result is as shown in table 1.
< absorbent commodity performance >
The preparation of (a) experimental liquid
In the container of 10L capacity, add appropriate distilled water, add sodium chloride 100g, calcium chloride dihydrate 3.0g and magnesium chloride hexahydrate 6.0g and dissolve.Secondly, add ethylene nonyl phenyl ether 0.25g, again add distilled water, the quality of entirety is adjusted to 10kg.And then, painted by No. 1 a small amount of, blueness, prepare experimental liquid.
The manufacture of (b) absorbent commodity
Use water-absorbing resins 10g and comminution pulp (Leonia society Leif Lock) 10g, make it mix equably by the air system of copying, thus made the absorber core portion of the sheet of the size of 42cm × 12cm.Then, by absorber core portion upper and lower with unit are grammes per square metre for 16g/m 2the paper handkerchief state of clamping under, by using roll-in entirety to be applied to make it compress in 30 seconds with the load of 196kPa, thus make absorber.In addition, on absorber, allocation unit area grammes per square metre is 22g/m 2polyethylene ventilation type cellular liquid permeability sheet material, below absorber, configure the polyethylene manufacture-illegal liquid permeability sheet material of formed objects, same units area grammes per square metre, by clamping absorber, as absorbent commodity A.In addition, absorbent commodity A is cut into the material of the size of 30cm × 12cm as absorbent commodity B.
Evaluation for liquid permeation rate and liquid back amount uses absorbent commodity A, and the evaluation for conformality (deformation time) uses absorbent commodity B.
(c) liquid permeation rate
The platform of level is placed absorbent commodity A.At the central part of absorbent commodity A, be placed on 10cm × 10cm, the center of plummet of 2kg possesses the measuring instrument that internal diameter is the throwing liquid cylinder of 3cm, by in disposable for the experimental liquid of 50mL this cylinder of input, use stopwatch simultaneously, mensuration to experimental liquid disappears completely the required time, as the time of penetration (second) of the 1st time in cylinder.Then, take off above-mentioned cylinder, absorbent commodity is maintained original state to preserve, to after 30 points and after 60 points from the experimental liquid of the 1st time drops into, on the position identical with the 1st time, all use measuring instrument to carry out identical operation, determine the time of penetration (second) of the 2nd time and the 3rd time.The total ascent time of 1st ~ 3 times is used as liquid permeation rate.Can say that liquid permeation rate is less, more preferred as absorbent commodity, such as, be preferably less than 400 seconds as liquid permeation rate, be more preferably less than 350 seconds.
(d) liquid back amount
To terminate and after 60 minutes from the mensuration of aforesaid liquid seepage velocity, experimental liquid on absorbent commodity A drops near position, place and determine quality (Wd (g) in advance, about 50g) the square filter paper of 10cm, this filter paper is placed the 5kg plummet that bottom surface is 10cm × 10cm.Make its load after 5 minutes, measure the quality (We (g)) of filter paper, using the quality of increase as liquid back amount (g).Can say that liquid back amount is less more preferred as absorbent commodity, such as, be preferably below 12g as liquid back amount, be more preferably below 10g.
Liquid back amount (g)=We-Wd
(e) conformality (deformation time)
At the immediate vicinity of absorbent commodity B, place the cylinder type cylinder that internal diameter is 3cm, by disposable for the experimental liquid of 150mL this cylinder of input, make it absorb.Then, from experimental liquid drops into after 5 minutes, with absorbent commodity B formed objects (unit are grammes per square metre 3500g/m 2) ground paper on place absorbent commodity B, by adhesive tape, ground paper and absorbent commodity B are fixed, put into UNIPACK (ユ ニ パ Star Network) (Co., Ltd. produces Japanese society production code member: K-4).Then, the absorbent commodity 7 of UNIPACK will be put into, being arranged on centrifugal force is as shown in Figure 2 set as on the rotating disk 6 of the diameter 30cm of 30G (425 revs/min), every one minute by visual confirmation, due to the distortion that the absorbent resin of the absorber in absorbent commodity B or the skew of comminution pulp etc. are caused, will confirm that the time of distortion is as deformation time.Mensuration proceeds to 40 minutes, the situation of the distortion of absorber unconfirmed, is defined as more than 40 minutes.Deformation time is the evaluation of estimate of conformality when representing that absorber is moistening, is preferably more than 35 minutes, is more preferably more than 40 minutes.
< evaluation result gather >
From the results shown in Table 1, the any one of the tan δ of the physiological saline water absorbing capacity of the water-absorbing resins obtained in embodiment 1 ~ 5 under physiological saline water holding capacity, 4.14kPa load and 50 times of swell gel demonstrates excellent numerical value, confirm absorbent commodity obtained in embodiments, in liquid permeation rate, liquid back amount and conformality (deformation time), possess superiority very.
On the other hand, the situation of the water-absorbing resins obtained in comparative example 1, although the physiological saline water absorbing capacity of water-absorbing resins under 4.14kPa load is high, but the numerical value of the tan δ of 50 times of swell gel is low, although the therefore excellence such as liquid back amount of absorbent commodity, but deformation time is short, and conformality is poor.In addition, for comparative example 2, the numeric ratio comparative example 1 of the tan δ of 50 times of swell gel is less, and therefore deformation time shortens.In addition, for the water-absorbing resins obtained in comparative example 3 and 4, the numerical value of the tan δ of 50 times of swell gel of water-absorbing resins is high, therefore the deformation time of absorbent commodity is long, and excellent shape retention property, but the physiological saline water absorbing capacity of water-absorbing resins under 4.14kPa load is low, gel blocking phenomenon occurs, and the liquid permeation rate of absorbent commodity is slack-off.Particularly for comparative example 4, the physiological saline water absorbing capacity of water-absorbing resins under 4.14kPa load is low, and it is many that the liquid of absorbent commodity returns quantitative change.For comparative example 5, the physiological saline water holding capacity of water-absorbing resins is low, and therefore to return quantitative change many for the liquid of absorbent commodity.
From then on result is known, is more than 38g/g, physiological saline water absorbing capacity under 4.14kPa load be the tan δ of more than 15mL/g and 50 times swell gel is 2.10 × 10 by making water-absorbing resins by physiological saline water holding capacity -2below integrally possess, can improve and use the whole of the liquid permeation rate of the absorber of water-absorbing resins and absorbent commodity, liquid back amount and conformality (deformation time), and make it possess excellent performance.
[table 1]
The explanation of Reference numeral
X determinator
1 buret portion
10 burets
11 air leading-in conduits
12 cocks
13 cocks
14 rubber bolt
2 conduits
3 measure platform
4 determination parts
40 cylinders
41 nylon wires
42 plummets
5 water-absorbing resins
6 rotating disks
7 absorbent commodities

Claims (11)

1. a water-absorbing resins, it is by water soluble alkene keyed unsaturated monomer in hydrocarbon dispersant, the water-absorbing resins that use radical polymerization initiator carries out inverse suspension polymerization and obtains,
It possesses the characteristic of following (1) ~ (3):
(1) physiological saline water holding capacity is more than 38g/g;
(2) the physiological saline water absorbing capacity under 4.14kPa load is more than 15mL/g;
(3) swelling 50 times time gel tan δ be 2.10 × more than 10-2.
2. water-absorbing resins according to claim 1, wherein,
Described water soluble alkene keyed unsaturated monomer for being selected from (methyl) acrylic acid and salt thereof, at least a kind in (methyl) acrylamide and N,N-DMAA.
3. water-absorbing resins according to claim 1 and 2, wherein,
Described water-absorbing resins is cross-linked by internal crosslinking agent and rear crosslinking agent.
4. water-absorbing resins according to claim 3, wherein,
The use amount of internal crosslinking agent, relative to the water soluble alkene keyed unsaturated monomer 1 mole paying polymerization, is 0.000015 ~ 0.00020 mole,
The use amount of rear crosslinking agent, relative to the water soluble alkene keyed unsaturated monomer 1 mole paying polymerization, is 0.00025 ~ 0.0010 mole.
5. the water-absorbing resins according to claim 3 or 4, wherein,
Internal crosslinking agent and rear crosslinking agent are multi-shrinking glyceryl compound.
6. an absorber, it contains water-absorbing resins according to any one of Claims 1 to 5 and hydrophilic fibre.
7. an absorbent commodity, it is formed between liquid permeability sheet material and liquid-impermeable sheet material for be remained on by absorber according to claim 6.
8. a manufacture method for water-absorbing resins, wherein,
Described water-absorbing resins possesses the characteristic of following (1) ~ (3),
(1) physiological saline water holding capacity is more than 38g/g;
(2) the physiological saline water absorbing capacity under 4.14kPa load is more than 15mL/g;
(3) swelling 50 times time gel tan δ be 2.10 × 10 -2above;
Further, the manufacture method of described water-absorbing resins comprises following first operation and the second operation:
First operation: in hydrocarbon dispersant, carries out the inverse suspension polymerization of water soluble alkene keyed unsaturated monomer under radical polymerization initiator and internal crosslinking agent exist;
Second operation: make it be cross-linked by rear crosslinking agent on the suspension polymerisation particle obtained in described first operation.
9. the manufacture method of water-absorbing resins according to claim 8, wherein,
Described water soluble alkene keyed unsaturated monomer is be selected from least a kind in (methyl) acrylic acid and salt, (methyl) acrylamide and N,N-DMAA.
10. the manufacture method of water-absorbing resins according to claim 8 or claim 9, wherein,
The use amount of the internal crosslinking agent in the first operation, relative to the water soluble alkene keyed unsaturated monomer 1 mole paying polymerization, is 0.000015 ~ 0.00020 mole;
The use amount of the rear crosslinking agent in the second operation, relative to the water soluble alkene keyed unsaturated monomer 1 mole paying polymerization, is 0.00025 ~ 0.0010 mole.
The manufacture method of the water-absorbing resins according to any one of 11. according to Claim 8 ~ 10, wherein,
Internal crosslinking agent and rear crosslinking agent are multi-shrinking glyceryl compound.
CN201380037722.8A 2012-09-10 2013-08-01 Water-absorbing resins, absorber and absorbent commodity Expired - Fee Related CN104507565B (en)

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Publication number Priority date Publication date Assignee Title
CN111542553A (en) * 2018-01-18 2020-08-14 住友精化株式会社 Water-absorbent resin
CN113166437A (en) * 2018-12-12 2021-07-23 住友精化株式会社 Water-absorbent resin particles
CN113242865A (en) * 2018-12-12 2021-08-10 住友精化株式会社 Water-absorbent resin particles
CN113544161A (en) * 2019-03-08 2021-10-22 住友精化株式会社 Water-absorbent resin particles, absorbent body, and absorbent article
CN113544164A (en) * 2019-03-08 2021-10-22 住友精化株式会社 Water-absorbent resin particles

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JP2003088552A (en) * 2001-09-19 2003-03-25 Sumitomo Seika Chem Co Ltd Absorber and absorptive article using it
CN1587289A (en) * 2004-07-09 2005-03-02 浙江大学 Process for preparing high water absorption resin
US20080280154A1 (en) * 2005-05-16 2008-11-13 Sumitomo Seika Chemicals Co., Ltd. Process for Producing Water-Absorbing Resin Particles, Water-Absorbing Resin Particles Made by the Process, and Absorbent Materials and Absorbent Articles Made by Using the Particles

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JP2003088552A (en) * 2001-09-19 2003-03-25 Sumitomo Seika Chem Co Ltd Absorber and absorptive article using it
CN1587289A (en) * 2004-07-09 2005-03-02 浙江大学 Process for preparing high water absorption resin
US20080280154A1 (en) * 2005-05-16 2008-11-13 Sumitomo Seika Chemicals Co., Ltd. Process for Producing Water-Absorbing Resin Particles, Water-Absorbing Resin Particles Made by the Process, and Absorbent Materials and Absorbent Articles Made by Using the Particles

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111542553A (en) * 2018-01-18 2020-08-14 住友精化株式会社 Water-absorbent resin
CN113166437A (en) * 2018-12-12 2021-07-23 住友精化株式会社 Water-absorbent resin particles
CN113242865A (en) * 2018-12-12 2021-08-10 住友精化株式会社 Water-absorbent resin particles
CN113544161A (en) * 2019-03-08 2021-10-22 住友精化株式会社 Water-absorbent resin particles, absorbent body, and absorbent article
CN113544164A (en) * 2019-03-08 2021-10-22 住友精化株式会社 Water-absorbent resin particles

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